Vladimir A. Kuimov

Addition of secondary phosphines to N-vinylpyrroles

Abstract Secondary phosphines 1 – 3 react readily with N -vinylpyrroles 4 and 5 under radical initiation to give regiospecifically anti-Markovnikov adducts, diorganyl-2-(1-pyrrolyl)ethylphosphines 6a – d , highly reactive building blocks for organic synthesis, in 88–91% yields.

Superbase-Assisted Addition of Phosphine to 1-Methoxy-4-vinylbenzene: Toward a Rare Family of Organic Phosphines

Abstract Phosphine reacts with 1-methoxy-4-vinylbenzene in the superbase suspension KOH-dimethylsulfoxide (70–100 °C, atmospheric pressure) to form regiospecifically anti-Markovnikov adducts, bis[2-(4-methoxyphenyl)ethyl]phosphine (1) and tris[2-(4-methoxyphenyl)ethyl]phosphine (2), representatives of rare arylalkylphosphines. The conditions for the selective preparation of phosphines 1 or 2 in 67% and 80% yields, respectively, have been elaborated. The phosphines have been oxidized with aqueous solution of H2O2, elemental sulfur, or selenium to afford the corresponding phosphine chalcogenides in good yields (95–99%). GRAPHICAL ABSTRACT

One-pot microwave synthesis of tertiary phosphine sulfides directly from aromatic alkenes, elemental phosphorus and sulfur in KOH–DMSO system

Aromatic alkenes (vinylbenzene, 1-(tert-butyl)-4-vinylbenzene, 1-chloro-4-vinylbenzene) react with red phosphorus and elemental sulfur in the superbasic system KOH–DMSO(H2O) under microwave irradiation (600 W, 6–8 min, Ar) in the presence of hydroquinone to afford tris(2-phenylethyl)-, tris[2-(4-tBu-phenyl)ethyl]- and tris[2-(4-Cl-phenyl)ethyl]phosphine sulfides in 53%, 38% and 42% yield, respectively. GRAPHICAL ABSTRACT

Reaction of Red Phosphorus with 4-Methoxystyrene in KOH-DMSO System: One-Pot Synthesis of Tris[2-(4-methoxyphenyl)ethyl]phosphane Oxide

Abstract Red phosphorus reacts with 4-methoxystyrene in the KOH-DMSO superbase system (130 °C, 3 h, Ar) in the presence of a small quantity of H2O to give tris[2-(4-methoxyphenyl)ethyl]phosphane oxide as the main product in 30% yield. Microwave activation of the reaction (600 W, 6 min) affords basically a mixture of the phosphane oxide and tris[2-(4-methoxyphenyl)ethyl]phosphane (in a ratio of 1:1). When the mixture is exposed to air (r.t., 24 h), the phosphane oxide is formed in 85% yield. GRAPHICAL ABSTRACT

Reactions of elemental phoshorus and phosphine with electrophiles in superbasic systems: XIX. Formation of the C-P bond with participation of elemental phosphorus under microwave assistance

Microwave irradiation facilitates phosphorylation of aryl methyl chlorides and styrene with red phosphorus in the presence of strong bases and increases the yield of the main products, tertiary phosphine oxides.

Synthesis of [2-(methoxyaryl)-1-methylethyl]phosphinic acids from red phosphorus and (allyl)(methoxy)benzenes

Abstract(Allyl)(methoxy)benzenes react with red phosphorus in the superbasic system KOH-DMSO in the presence of small amounts of water and hydroquinone (3 h, 130 °C) to regio- and chemoselectively give [2-(methoxyaryl)-1-methylethyl]phosphinic acids in preparative yields up to 52%. The reactions involve isomerization of allylbenzenes into (prop-1-enyl)benzenes.

Phosphorylation of Allyl Halides with White Phosphorus

White phosphorus reacts with allyl bromide in the system KOH-dioxane-H 2 O at room temperature to form tris(propen-2-yl), bis(propen-2-yl)(E-propen-1-yl), and bis(E-propen-1-yl)(propen-2-yl)phosphine oxides in a total quantitative yield, their molar ratio being 1:0.5:0.1.

Reactions of elemental phosphorus and phosphine with electrophiles in superbasic systems: XVIII. Phosphorylation of 1-(chloromethyl)naphthalene with the elemental phosphorus

Abstract1-Chloromethylnaphthalene reacts with white and red phosphorus, and also with the “activated red phosphorus,” the complex organophosphorus polymer of unknown structure obtained by irradiation of a solution of white phosphorus in benzene by the 60Co source, in a system including KOH water solution, dioxane or benzene, and a phase transfer catalyst (22–98°C, argon), to form bis(1-naphthylmethyl)-and tris-(1-naphthylmethyl)phosphine oxides, and also (1-naphthylmethyl)phosphonous-and bis(1-naphthylmethyl)-phosphinic acids. The yield and the ratio of the reaction products depend on reaction conditions as well as on the nature of phosphorylating agent. It is shown that the reactivity of the “activated red phosphorus” is not worse than that of the white phosphorus and significantly exceeds the reactivity of the usual technical red phosphorus.

Microwave synthesis of secondary phosphines and phosphine oxides from red phosphorus and allyl(methoxy)benzenes in KOH-DMSO

Bis[1-(methoxyphenyl)propan-2-yl]phosphines and bis[1-(methoxyphenyl)propan-2-yl]phosphine oxides were synthesized by phosphorylation of allyl(methoxy)benzenes in the system red phosphorus-KOH · 0.5 H2O-DMSO under microwave irradiation.

Reaction of Activated Red Phosphorus with Allyl Bromide under Phase-Transfer Catalysis

Common red phosphorus (Pn) reacts with allyl halides (bromide and chloride) on heating (45 75 C) under phase-transfer catalysis to form mixtures of tertiary unsaturated phosphine oxides (total yield up to 23%), among which products of prototrophic isomerizations of tri(propen-2-yl)phosphine oxide (I) prevail. These are di(propen-2-yl)[(E)-propen-1-yl]-, di(propen-2-yl)[(Z)-propen-1-yl]-, (propen-2-yl)[(E)propen-1-yl][(Z)-propen-1-yl]-, di[(E)-propen-1-yl](propen-2-yl)-, di[(Z)-propen-1-yl](propen-2-yl)-, tri[(E)-propen-1-yl]-, and di[(E)-propen-1-yl][(Z)-propen1-yl]phosphine oxides [1]. At room temperature this reaction gives mainly the kinetically controlled product, phosphine oxide I, in a yield less than 2% (in this case, the phosphorus conversion is 18%) [1].